U.S. patent number 4,532,266 [Application Number 06/360,037] was granted by the patent office on 1985-07-30 for polymer-containing polyether polyamines and a process for the production of these polyamines.
This patent grant is currently assigned to Bayer Aktiengesellschaft. Invention is credited to Gerhard Balle, Dieter Dieterich, Holger Meyborg, Werner Rasshofer.
United States Patent |
4,532,266 |
Rasshofer , et al. |
July 30, 1985 |
Polymer-containing polyether polyamines and a process for the
production of these polyamines
Abstract
Polyether-based urethane-group-containing polyamines containing
polymers and/or copolymers of unsaturated monomers and, optionally,
urea and/or biuret and/or allophanate groups are produced by (a)
reacting an NCO-prepolymer in aqueous alkaline solution at
0.degree. to 40.degree. C. to form a carbamate; (b) converting this
carbamate to an amine by adding an ion exchanger to the reaction
mixture; and (c) separating the polyamine from the reaction
mixture. The NCO-prepolymers used as starting materials are
prepolymers of (i) polyalkylene ether polyols having a molecular
weight of from 1,000 to 10,000 containing from 1 to 60 wt. % of
graft (co)polymers of unsaturated monomers; and (ii) excess molar
quantities of organic polyisocyanate; and optionally, (iii) a low
molecular weight chain-extending agent. The product polyamines have
a molecular weight of from 1,000 to 10,000 and contain from 0.65 to
59.3 wt. % graft (co)polymer and from 0.11 to 2.9 wt. % terminal
NH.sub.2 groups attached to the ethers by urethane groups in the
polyisocyanate. The product polyamines are particularly useful in
the production of polyurethanes.
Inventors: |
Rasshofer; Werner (Cologne,
DE), Balle; Gerhard (Leverkusen, DE),
Dieterich; Dieter (Leverkusen, DE), Meyborg;
Holger (Odenthal, DE) |
Assignee: |
Bayer Aktiengesellschaft
(Leverkusen, DE)
|
Family
ID: |
6128460 |
Appl.
No.: |
06/360,037 |
Filed: |
March 19, 1982 |
Foreign Application Priority Data
|
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Mar 27, 1981 [DE] |
|
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3112118 |
|
Current U.S.
Class: |
521/159; 521/134;
521/137; 528/482; 528/489; 528/60; 528/64; 528/68; 560/157;
560/159; 560/24; 564/38; 564/511; 564/512; 564/57; 564/59;
564/61 |
Current CPC
Class: |
C08G
18/10 (20130101); C08G 18/12 (20130101); C08G
18/5048 (20130101); C08G 18/632 (20130101); C08G
18/10 (20130101); C08G 18/305 (20130101); C08G
18/12 (20130101); C08G 18/302 (20130101) |
Current International
Class: |
C08G
18/00 (20060101); C08G 18/63 (20060101); C08G
18/10 (20060101); C08G 18/12 (20060101); C08G
18/50 (20060101); C07C 127/15 (); C07C
127/24 () |
Field of
Search: |
;521/137,134,159
;528/60,64,482,489 ;560/157,24,159 ;564/38,57,59,61,511,512 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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55-007825 |
|
Jan 1980 |
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JP |
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1033912 |
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Jul 1963 |
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GB |
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1117494 |
|
Dec 1965 |
|
GB |
|
Primary Examiner: Kight; John
Assistant Examiner: Moore; M. L.
Attorney, Agent or Firm: Harsh; Gene Gil; Joseph C. Whalen;
Lyndanne M.
Claims
What is claimed is:
1. A process for the production of a polyetherbased,
urethane-group-containing polyamine which contains a polymer and/or
copolymer of an unsaturated monomer comprising:
(a) converting a urethane-group-containing NCO-prepolymer of
(i) a difunctional or polyfunctional polyalkylene ether polyol
having a molecular weight of from 1,000 to 10,000 which polyol
contains from 1 to 60 wt. % of a grafted-on polymer and/or
copolymer of an unsaturated monomer with
(ii) an excess molar quantity of an organic polyisocyanate into the
corresponding carbamate in aqueous dispersion by reacting the
prepolymer with an alkaline aqueous medium at a temperature of from
0.degree. to 40.degree. C. in a quantity such that the equivalent
ratio of OH.sup..crclbar. groups to NCO groups is greater than 1.01
to 1;
(b) converting the thus-produced carbamate into an amine by adding
an equivalent or slightly greater than equivalent quantity of an
acid ion exchanger; and
(c) separating the thus-produced urethane-group-containing polymer
polyether polyamine from the reaction mixture.
2. The process of claim 1 wherein the polyalkylene ether prepolymer
additionally contains urea and/or biuret and/or allophanate
groups.
3. The process of claim 1 wherein the reactants converted in step
(a) include a lower molecular weight chain-extending agent having a
molecular weight of from 18 to 400.
4. The process of claim 1 wherein an inert water-miscible organic
solvent is employed in step (a).
5. The process of claim 1 wherein the NCO-prepolymer is made from a
difunctional or trifunctional polyalkylene ether polyol having a
molecular weight of from 2,000 to 6,000 which polyol contains from
5 to 40 wt. % graft polymer and/or copolymer of an unsaturated
monomer.
6. The process of claim 1 or 5 in which the graft polymer and/or
copolymer used is based on a monomer selected from the group
consisting of acrylonitrile, methacrylonitrile, styrene,
.alpha.-methyl styrene, acrylic acid alkyl ester, methacrylic acid
alkyl ester and mixtures thereof.
7. The process of claim 1 or 5 in which the graft copolymer is
based on acrylonitrile with styrene or methacrylic acid methyl
ester.
8. The process of claim 1 wherein the NCO-prepolymer is prepared
with a quantity of polyisocyanate such that the NCO/OH-ratio is
from 1.5:1 to 2.8:1.
9. The process of claim 1 wherein the polyisocyanate is modified by
urea and/or biuret and/or allophanate groups.
10. The process of claim 1 wherein the alkaline aqueous medium is
an alkali hydroxide solution in which a hydroxyl ion/NCO group
ratio of from 1.01:1 to 1.6:1 is maintained.
11. The process of claim 1 wherein from 1.01 to 2 equivalents of
hydrogen ions emanate from the ion exchanger for each equivalent of
alkali.
12. A urethane-group-containing polymer polyether polyamine based
on polyalkylene ether residues having a molecular weight of from
1,000 to 10,000, a graft polymer or copolymer content of from 0.65
to 59.3 wt. %, and from 0.11 to 2.9 wt. % terminal NH.sub.2 groups
attached to the polyalkylene ether residue by a urethane group in
the organic polyisocyanate.
13. A process for the production of polyurethane plastics,
elastomers and foams comprising:
(a) converting a urethane-group-containing NCO-prepolymer of
(i) a difunctional or polyfunctional polyalkylene either polyol
haing a molecular weight of from 1,000 to 10,000 which polyol
contains from 1 to 60 wt. % of a grafted-on polymer and/or
copolymer of an unsaturated monomer with
(ii) an excess molar quantity of an organic polyisocyanate into the
corresponding carbamate in aqueous dispersion by reacting the
prepolymer with an alkaline aqueous medium at a temperature of from
0.degree. to 40.degree. C. in a quantity such that the equivalent
ratio of OH.sup..crclbar. groups to NCO groups is greater than 1.01
to 1;
(b) converting the thus-produced carbamate into an amine by adding
an equivalent or slightly greater than equivalent quantity of an
acid ion exchanger;
(c) separating the thus-produced urethane-group-containing polymer
polyether polyamine from the reaction mixture; and
(d) reacting the polymer polyether polyamine separated in (c) with
a polyisocyanate.
Description
BACKGROUND OF THE INVENTION
This invention relates to polyether-based,
urethane-group-containing polyamines which contain polymers and/or
copolymers of unsaturated compounds, preferably in the form of
graft polymers, and optionally urea and/or biuret and/or
allophanate groups. The invention also relates to a process for the
production of such polyamines by the hydrolysis of NCO-prepolymers
containing terminal isocyanate groups.
Polyamines containing urethane groups are known to those in the
art. German Auslegeschrift No. 1,270,046 for example, describes a
process for the production of specific primary aromatic amines
containing polyalkylene glycol ether segments in which reaction
products of aromatic diisocyanates or triisocyanates with
polyalkylene glycol ethers and/or polyalkylene glycol thioethers
are reacted with secondary or tertiary carbinols. The products of
this reaction are subsequently subjected (optionally in the
presence of acid catalysts) to thermal decomposition in an inert
solvent. One of the disadvantages of this process is that thermal
decomposition of the urethanes is accompanied by formation of
combustible, readily volatile alkenes which are explosive in
admixture with air. Precautionary measures must therefore be
taken.
German Auslegeschrift No. 1,694,152 relates to the production of
prepolymers containing at least two terminal amino groups by
reacting hydrazine, aminophenyl ethyl amine or other diamines with
an NCO-prepolymer of a polyether polyol and a polyisocyanate
(NCO/NH-ratio=1:1.5 to 1:5). In this process, unreacted amine has
to be carefully removed in an additional step because it catalyzes
the reaction with polyisocyanates to a considerable extent (thus
leading to short processing times) and may act as a reactant.
Another process for synthesizing polyamines containing urethane
groups is described in French Pat. No. 1,415,317. In this process,
NCO-prepolymers containing urethane groups are converted with
formic acid into the N-formal derivatives which are then hydrolyzed
to form terminal aromatic amines. The reaction of NCO-prepolymers
with sulfamic acid in accordance with German Auslegeschrift No. 1
155 907 (U.S. Pat. No. 3,184,502) also gives compounds containing
terminal amino groups. Relatively high molecular weight,
prepolymers containing aliphatic secondary and primary amino groups
are obtained in German Auslegeschrift No. 1,215,373 by reacting
hydroxyl compounds of relatively high molecular weight with ammonia
in the presence of catalysts under pressure at elevated
temperatures. Such prepolymers are made in U.S. Pat. No. 3,044,989,
by reacting polyhydroxyl compounds of relatively high molecular
weight with acrylonitrile followed by catalytic hydrogenation.
According to German Offenlegungsschrift No. 2,546,536 and U.S. Pat.
No. 3,865,791, relatively high molecular weight compounds
containing terminal amino groups and urethane groups are also
obtained by reacting NCO-prepolymers with enamines, aldimines or
ketimines containing hydroxyl groups, followed by hydrolysis.
It is known that aromatic isocyanates can be converted into primary
amines by acid hydrolysis. However, the reaction is far from
complete because the amine formed during hydrolysis reacts further
with unreacted isocyanate to form the corresponding urea. This
further reaction cannot be suppressed even by using excess strong
mineral acid. (See, e.g., Japanese Patent No. 55007-825).
It is also known that polyurethanes which have been produced from
so-called polymer polyols, which are polyether polyols
graft-modified by polymers or copolymers of olefinically
unsaturated monomers, are distinguished by an improved property
level. In particular, the hardness and durability of flexible
polyurethane foams is favorably affected so that low unit weights
can be adjusted and savings made on raw materials. Additionally,
these polymer polyols provide flexible foams with more open cells
and, as a result, counteract shrinkage of fresh foams during
storage. Finally, it is possible to use polymer polyols (provided
that the basic polyether is suitably selected) to produce so-called
highly elastic, cold-hardening foams. In contrast to conventional
processes for the production of foams of this type, there is no
need to use special polyisocyanates characterized by balanced
reactivity. It is therefore possible to use standard commercial
products, particularly the tolylene diisocyanate used predominantly
in the manufacture of flexible foams.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for
the production of polyether-based urethane group-containing
polyamines containing polymers or copolymers of unsaturated
compounds grafted onto the polyether (hereinafter referred to as
"polymer polyether polyamines").
It is also an object of the present invention to provide a
technically simple process for the production of polymer polyether
polyamines.
It is another object of the present invention to provide new
polymer polyether polyamines which are particularly useful in the
production of polyurethanes.
These and other objects which will become apparent to those skilled
in the art are accomplished by reacting an NCO-prepolymer of a
specific type in an alkaline aqueous medium at a temperature of
from 0.degree. to 40.degree. C. to form the corresponding
carbamate. This carbamate is then converted to an amine by means of
an ion exchanger. The polymer polyether polyamine thusproduced is
based on polyalkylene ether residues having a molecular weight of
from 1,000 to 10,000, a graft polymer or copolymer content of from
0.65 to 59.3 wt. % and from 0.11 to 2.9 wt. % terminal NH.sub.2
groups attached to the polyalkylene ether residue by a urethane
group in the organic polyisocyanate.
DETAILED DESCRIPTION OF THE INVENTION
The polymer polyether polyamines of the present invention may be
directly obtained by introducing corresponding NCO-prepolymers
dropwise into excess aqueous alkaline medium, treating the alkali
carbamates formed with acid ion exchanger and thus converting the
NCO-groups into amino groups. This is an unexpectedly smooth
reaction which does not involve any problems in terms of process
technology.
More specifically, the polyether-based, urethane-group-containing
polyamines, which contain polymers and/or copolymers of unsaturated
monomers and, optionally, urea and/or biuret and/or allophanate
groups, are produced by hydrolyzing urethane-group-containing
NCO-prepolymers of (i) a bifunctional or higher functional
polyalkylene ether polyol having a molecular weight of from 1,000
to 10,000 (preferably from 2,000 to 6,000) which contains from 1 to
60 wt. % (preferably from 5 to 40 wt. %, most preferably from 10 to
30 wt. %) of grafted-on polymer(s) and/or copolymer(s) of an
unsaturated monomer and optionally, urea, biuret and/or allophanate
groups, and (ii) an excess molar quantity of an organic
polyisocyanate, and optionally (iii) a low molecular weight
chain-extending agent having a molecular weight of from 18 to 400.
This prepolymer is converted into the corresponding carbamate in
aqueous dispersion by introducing the prepolymer into an alkaline
aqueous medium, (optionally in the presence of an inert
water-miscible organic solvent) at a temperature in the range from
0.degree. to 40.degree. C., preferably from 10.degree. to
25.degree. C. The equivalent ratio between OH-groups and NCO-groups
should be greater than 1.01:1. The thus-produced carbamate is then
converted into an amine with elimination of carbon dioxide by the
addition of an equivalent or excess quantity of an acid ion
exchanger. The polymer polyether polyamine containing urethane
groups thus obtained is subsequently separated off from the
reaction mixture in accordance with techniques known to those in
the art.
The present invention also relates to polyalkylene-ether-based,
urethane-group-containing polyamines containing aliphatic and/or
aromatic amino groups obtained by the hydrolysis of corresponding
NCO-prepolymers and containing graft polymers or copolymers of
unsaturated monomers and, optionally, urea and/or biuret and/or
allophanate groups.
The polymer polyether polyamines of the present invention may be
synthesized from polyalkylene ether polyol residues having a
molecular weight of from 1,000 to 10,000 (preferably from 2,000 to
6,000) which contain grafted-on polymers and/or copolymers of
unsaturated compounds in quantities of from 1 to 60 wt. %
(preferably from 5 to 40 wt. %, most preferably from 10 to 30 wt.
%) and in which terminal amino groups are attached to the polyether
by urethane groups of the polyisocyanate.
The polymer polyether polyamines of the present invention contain
from 2.9 to 0.11 wt. % (preferably from 1.7 to 0.18 wt. %) of free
NH.sub.2 -groups so the functionality is generally from 2 to 3.
These polymer polyether polyamines have a polymer content of from
0.65 to 59.3 wt. %, preferably from 0.8 to 59 wt. % and most
preferably from 9.35 to 28 wt. %.
The amino groups of the polyether polyamines of the present
invention may be attached to aliphatic, cycloaliphatic or,
preferably, aromatic residues derived from aliphatic,
cycloaliphatic or aromatic polyisocyanates in the production of the
prepolymers with the polymer polyols. These residues of the
isocyanates are attached by means of urethane groups to the
polymer-containing polyether polyol residues (formed from polyols
and isocyanates).
Where the NCO-prepolymers still contain urea, biuret and/or
allophanate groups (either in the starting material itself or
formed during the reaction in which the NCO-prepolymer is formed),
these groups are also present in the product polyamines because the
process of the present invention involves a non-destructive
hydrolysis reaction and careful working up of the reaction
products.
The present invention also relates to the use of the
polyalkylene-ether-based, urethane-group-containing polyamines
containing graft polymers of unsaturated monomers and optionally
urea and/or biuret and/or allophanate groups obtainable by the
process of the present invention as synthesis components in the
production of homogeneous and/or cellular polyurethane plastics and
foams. Such polyurethanes may be formed by reacting polyisocyanates
with the polymer polyether polyamines of the present invention and
optionally other low molecular weight and/or relatively high
molecular weight compounds containing isocyanate-reactive groups,
optionally in the presence of known additives and auxiliaries.
The process of the present invention is particularly surprising
because in the production of NCO-prepolymers from polyisocyanates
and NCO-reactive compounds containing H-atoms, traces of monomeric
isocyanate often remain in the prepolymer. In the process of the
present invention, however, it is only the corresponding low
molecular weight polyamines which form complexes with the ion
exchanger and which can be removed with the ion exchanger from the
reaction mixture. Surprisingly, however, this association with the
ion exchanger does not occur with polyamines of relatively high
molecular weight. Consequently, polymer polyether polyamines of
relatively high molecular weight may be obtained directly (rather
than through formation of mineral acid salts) and with considerably
improved molecular consistency in the process of the present
invention.
The process of the present invention is advantageous because the
ion exchanger may be added to the carbamate solution or suspension
or vice versa without affecting the results. Further, there is
nothing in the least aggressive about the process of the present
invention. Consequently, the product polyamines (including aromatic
polyamines) are generally obtained in the form of colorless to pale
yellowish products which due to the absence of impurities, oxidize
and discolor far more slowly than polyamines prepared by other
processes. In fact, the process of the present invention is so mild
that even senstitive, biuret-group-containing and/or
allophanate-group-containing polyamines may be produced without any
difficulty.
It is possible to use more than the equivalent quantity of acid ion
exchanger (based on the H-atoms) without the relatively high
molecular weight polyamines being converted into the corresponding
salts. However, this would necessitate an additional process step
in which the undesirable salt is accumulated as is the case where
the decomposition of the carbamates is carried out with excess
mineral acid.
In accordance with the present invention, the NCO-prepolymers used
as starting materials may be obtained from polymer polyols of the
type obtained by the radical in situ polymerization of unsaturated
compounds ("monomers") in the presence of bifunctional and/or
higher functional polyalkylene oxide polyols (polyethers). One or
more vinyl monomers are generally used for this purpose. Such vinyl
monomers include styrene, methyl styrene, acrylonitrile,
methacrylonitrile, acrylic acid alkyl ester, methacrylic acid alkyl
ester and other known monomers, optionally in modifying quantities.
It is preferred to use styrene, .alpha.-methyl styrene,
acrylonitrile and (meth)acrylic acid methyl ester. Copolymers of
styrene and acrylonitrile are particularly preferred.
The production of polyether polyols modified by polymers or
copolymers is known. Such modified polyether polyols may be
obtained by grafting polymer-modified polyether polyols, although
ungrafted polymers may also be present in the mixture. The
production and use of polymer polyols of this type are described
for example in U.S. Pat. Nos. 3,304,273 and 2,383,351; in German
Auslegeschrift No. 2,915,260; German Pat. Nos. 1,222,660, 1,152,536
and 1,152,537; and also in the article by F. E. Critchfield et al
in Rubber Chemistry and Technology, 45 (1972), pages 1467 to 1481.
The polyethers which are used to be modified with polymers by
polymerisation of monomers are known and generally contain from 2
to 8 (preferably 2 to 3) hydroxyl groups. Such polyethers may be
obtained for example by polymerizing epoxides, such as ethylene
oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene
oxide or epichlorohydrin. Polyethers may also be produced by
addition of epoxides (preferably ethylene oxide or propylene
oxide), optionally in admixture, in any ratio or successively with
starter components containing reactive hydrogen atoms. Suitable
compounds containing reactive hydrogen atoms are water, alcohols,
ammonia and amines. Examples of these include ethylene glycol,
1,2-propylene glycol, trimethylol propane, glycerol, sorbitol,
4,4'-dihydroxy diphenyl propane, aniline, ethanolamine,
diethanolamine, N-methyl diethanolamine and ethylene diamine.
Sucrose polyethers and formitol- or formose-started polyethers may
also be used to modify polymers with monomers. In many cases, it is
preferred to use polyethers of the type which contain predominantly
primary OH-groups (up to 90 wt. % based on all the OH-groups
present in the polyether). The polyalkylene oxide polyols based on
ethylene oxide, propylene oxide and tetrahydrofuran are
preferred.
The difunctional and higher functional polyether polyols used in
the practice of the present invention should have a molecular
weight in the range from about 1,000 to 10,000, preferably in the
range from 2,000 to 6,000 and a functionality of preferably from 2
to 3.
The polymer content of the polymer polyether polyols used to form
the NCO prepolymers required in the present invention should amount
to between 1 and 60 wt. % of polymer (preferably in grafted form),
preferably between 5 and 40 wt. % and most preferably, between 10
and 30 wt. % based on the polyether polymer end product.
Low molecular weight, H-active compounds having a molecular weight
of from 18 to about 400 may optionally be used in small quantities
in the reaction of the polymer polyols with the polyisocyanates to
form the NCO-prepolymer. These compounds, which are also known as
chain-extending agents, should be used in quantities of less than
0.5 mole and preferably in quantities of from 0.01 to 0.2 mol per
mole of polymer polyol. Suitable compounds of this type are water;
diols, such as ethylene glycol, 1,2-propylene glycol, 2,3-butane
diol and/or 1,4-butane diol, neopentyl glycol; isophorone diamine;
neopentyl diamine; 2,4- and/or 2,6-tolylene diamine;
tetraalkyl-dicyclohexyl methane-2,4'- and/or -4,4'-diamines;
polyethylene oxide; propylene oxide; and tetramethylene oxide diols
having molecular weights below 400. Use of these chain-extending
agents makes it possible to incorporate other urethane and/or urea
groups and possibly allophanate or biuret groups (formed during the
reaction with the polyisocyanates) into the NCO-prepolymer.
Suitable polyisocyanates for the practice of the present invention
are aliphatic, cycloaliphatic, araliphatic, aromatic and
heterocyclic polyisocyanates free from hydrolyzable groups (apart
from NCO-groups), of the type described in detail for example on
pages 8 to 11 of German Offenlegungsschrift No. 2,854,384.
Preferred polyisocyanates are diisocyanates such as
1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,
1,12-dodecane diisocyanate; cycloaliphatic diisocyanates in the
form of mixtures of their position- and/or stereo-isomers such as
cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and
1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl
cyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate,
hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4'-
and/or -4,4'-diphenyl methane diisocyanate. However, aromatic
diisocyanates are particularly suitable. Examples of these
diisocyanates are 1,3- and 1,4-phenylene diisocyanate, 2,4- and
2,6-tolylene diisocyanate and mixtures of these isomers, diphenyl
methane-2,4'-, -2,2'- and/or -4,4'-diisocyanate, including its
alkyl- and chlorine-substitued derivates and
naphthylene-1,5-diisocyanate. It is also possible to use
polyphenyl-polymethylene-polyisocyanates of the type obtained by
condensing aniline with formaldehyde and then phosgenating the
condensation product. Polyisocyanates containing isocyanurate
groups, urethane groups, acylated urea groups, allophanate groups
and biuret groups may also be used.
It is particularly preferred to use polyisocyanates having
different degrees of reactivity between their NCO-groups. Such
polyisocyanates include araliphatic diisocyanates or aromatic
diisocyanates, such as tolylene-2,4-diisocyanate, diphenyl
methane-2,4'-diisocyanate, 3',5'-dimethyl diphenyl
methane-2,4'-diisocyanate, 3',5'-dimethyl diphenyl
methane-4,4'-diisocyanate and
3,5-dimethyl-3',5'-diisopropyl-4,4'-diisocyanate. The diisocyanate
most preferably used on a commercial scale is
tolylene-2,4-diisocyanate.
The NCO-prepolymers containing terminal isocyanate groups used in
the hydrolysis reaction of the present invention may be produced in
known manner by reacting the reactants either as a melt or in
solution. In either case, the equivalent ratio of NCO-groups to
active hydrogen atoms (preferably OH-groups) is greater than 1 and
should generally be between 1.5:1 and 2.8:1. It is of course
possible to use an even larger excess of polyisocyanate, for
example 10:1. Any excess polyisocyanate may be removed by
thin-layer evaporation, leaving NCO-prepolymers having a
composition which is relatively close to two equivalents of
NCO-groups for each equivalent of active hydrogen.
The prepolymers are generally oily to wax-like in consistency,
depending upon the starting components selected. If the NCO/OH
ratio is greater than 2, non-extended prepolymers are generally
obtained. If the NCO/OH-ratio is less than 2, the average molecular
weight of the NCO-prepolymers will increase and urethane groups
will become attached thereto.
It is also possible to use low molecular weight polyols or other
chain-extending agents in small quantities (in addition to the
relatively high molecular weight polymer polyethers) in the
production of the prepolymers. When these materials are used, the
prepolymers obtained are also of relatively high molecular
weight.
Where the starting components include diamines as chain-extending
agents or urea-containing, biuret-containing or
allophanate-containing polyisocyanates, these groups are also
incorporated into the NCO-prepolymers. Allophanate and biuret
groups can also be formed from the reaction of urea or
urethane-containing prepolymers under rigorous reaction conditions.
In either case, urethane groups are present in the NCO-prepolymer
as a result of the linking reaction between the polymer polyether
polyol and the polyisocyanate.
In the process of the present invention, the NCO-prepolymers are
generally first dissolved in an inert organic solvent which solvent
is at least partly miscible with water. Suitable solvents are, for
example, dimethoxy ethane (DME), tetrahydrofuran and dioxane. For
example, from 1 to 400 parts of the NCO-prepolymer may be used for
each 100 parts of solvent. It is generally best to introduce the
prepolymer slowly with stirring (preferably over a period of 30 to
120 minutes) into a solution of alkali or alkaline-earth hydroxides
in water and/or another water-miscible solvent free from NCO-active
hydrogen atoms at between about 0.degree. and 40.degree. C.,
preferably to between 10.degree. and 25.degree. C. The
concentration of these alkali (or alkaline-earth) materials should
preferably be 1 part by weight of base to between 2 and 20 parts by
weight of water or solvent. Solutions of inorganic and organic
ammonium hydroxides (for example tetra-alkyl ammonium hydroxide)
are also suitable. From 5 to 20 wt. % alkali hydroxide solutions
are preferable.
If no solvent is used, the viscosity of the NCO-prepolymer should
be as low as possible (preferably up to about 500 mPas). At
sufficiently low viscosities, the prepolymer may have to be
preheated (for example to between 30.degree. and 90.degree. C.)
before it is added to the alkali or alkaline-earth material. The
prepolymer should be added with vigorous stirring in the finest
possible distribution (for example by injection through a nozzle
under pressure). The amount of water initially introduced may be
increased by a factor of from 1.1 to 100 to make stirring
easier.
The quantity in which the alkali (alkaline-earth) hydroxide is used
or the quantity in which the bases are used should be such that at
least a small quantity of free base is left on completion of the
reaction. An NCO/OH-ion ratio of from 1:1.01 to 1:1.60 and use of
alkali hydroxides are preferred for this purpose. The concentration
of residual base should not be too high because urethane groups
present in the prepolymer after formation of the carbamate would
also be hydrolyzed. In order to improve the homogeneity of the
solutions, it is preferred to add a standard commercial emulsifier
in quantities of from 0.1 to 1 part by weight and preferably in a
quantity of approximately 0.5 part by weight (per 100 parts of
reaction mixture). Intensive stirring is advisable when the
NCO-component is being mixed with the hydroxide component in order
to avoid local imbalances in concentration. After the prepolymer
has been added, the mixture should be stirred for another 5 to 180
minutes and preferably for 10 to 60 minutes at 0.degree. to
40.degree. C.
It may be advantageous to lower the viscosity of the carbamate
prior to treatment with the ion exchanger. The viscosity may be
lowered by dilution with a suitable solvent. Suitable solvents are
dioxane, tetrahydrofuran, acetonitrile, methanol, ethanol,
i-propanol. Methanol is preferred.
In the second step of the process of the present invention, the
carbamate solution or carbamate suspension is combined with an ion
exchanger. It does not matter whether the acid ion exchange resin
is added to the carbamate suspension or carbamate solution or
whether the reverse procedure is adopted. The ion exchange resin
and the carbamate should be combined with one another at a rate
commensurate both with the intensity of the evolution of gas and
with the dimensions of the apparatus. Periods of from 1 to 300
minutes, particularly 10 to 90 minutes may be appropriate. The
evolution of gas generally begins only after about one quarter of
the total quantity of ion exchange resin has been added. However,
the evolution of gas is not sudden or violent, but takes place
steadily and is easy to control. When the components are combined,
there should be little or no increase in temperature. A temperature
change of from 10.degree. to 70.degree. C. (which may have to be
adjusted by external heating) has been found to be acceptable.
The exchanger should be added until there is no further evolution
of gas. Brief heating to 60.degree.-110.degree. C. should drive out
any dissolved carbon dioxide.
The acid ion exchange resin should be used in a quantity which is
at least sufficient to neutralize the base used in the first stage
of the process. In general, however, it is desirable to use a small
excess of protons emanating from the acid ion exchange resin. From
1.01 to 2 equivalents of hydrogen ions are generally used for each
equivalent of base (expressed as OH).
The reverse procedure (i.e., addition of carbamate to the ion
exchanger) is preferred when the reaction data are known and where
the process is carried out continuously. On completion of the ion
exchange reaction, the reaction mixture is basic due to the
presence of free amine and its base strength.
Ion exchangers suitable for use in the process of the present
invention include any substances which contain labile acid hydrogen
atoms in an insoluble polymeric skeleton. Polymeric acids that are
particularly suitable for use in the process of the present
invention are ion exchange resins which have as their polymeric
base a styrene/divinyl benzene skeleton to which base sulfonic acid
groups are attached as acid functions. Other polymeric acids which
may be used are ion exchange resins which have a polyacrylate
skeleton as their polymeric base to which base carboxylic acid
anchor groups are attached.
The reaction mixture may then be treated to remove spent ion
exchanger (e.g., by filtration). The solvent may be removed by
distillation under reduced pressure, for example under a pressure
of from 0.01 to 700 Torr. The spent ion exchange resins (neutral
form) may be regenerated by known methods and reused without
difficulty. All the polymer polyether polyamines thus-obtained may
be freed from traces of volatile constituents at 0.01 to 0.1
Torr/60.degree.-80.degree. C.
Due to their low vapor pressure, the polymer polyether polyamines
of the present invention may advantageously be used as
polyisocyanate reactants in the production of optionally cellular
polyurethane plastics. These polymer polyether polyamines may be
used alone or in combination with other low molecular weight
(molecular weight 32-399) and/or relatively high molecular weight
(molecular weight 400 to approximately 15,000) compounds containing
isocyanate-reactive groups to produce polyurethanes. The polymer
polyether polyamines of the present invention are particularly
suitable for high-frequency-weldable polyurethane-based flexible
foam plastics.
The polyamines of the present invention may also be used as
coupling components for diazo dyes, hardeners for epoxide and
phenolic resins and any other known reactions involving amines
(such as amide-forming or imide-forming reactions, etc.).
Homogeneous and/or cellular polyurethane plastics and elastomers or
foams, may be produced from the polymer polyether polyamines of the
present invention in known manner with materials normally used for
making such polyurethanes (see for example, German
Offenlegungsschrift Nos. 2,302,564; 2,432,764; 2,512,385;
2,513,815; 3,550,796; 2,550,797; 2,550,833; 2,550,860; 2,550,862
and 2,639,083).
The compounds identified above as being useful for production of
the NCO-prepolymers may also be used as a polyisocyanate reactant
in the production of polyurethanes. Further examples are aliphatic,
cycloaliphatic, araliphatic, aromatic and heterocyclic
polyisocyanates. Polyisocyanates which have been further modified
as described on pages 8 to 11 of German Offenlegungsschrift No.
2,854,384 may also be employed.
Compounds containing at least two isocyanate-reactive hydrogen
atoms and having a molecular weight of generally from 62 to 10,000
(for each individual component) may be employed in the usual way as
polyol starting components for the production of the homogeneous or
cellular polyurethane plastics and elastomers or foams (including
integral foams). It is preferred that compounds containing hydroxyl
groups, particularly compounds of relatively high molecular weight
containing from 2 to 8 hydroxyl groups, preferably compounds having
molecular weights in the range from 400 to 8,000 and most
preferably in the range from 600 to 6,000 be used as the
predominant reactive hydrogen-containing compound. Examples of such
compounds are polyesters, polyethers, polythioethers, polyacetals,
polycarbonates and polyester amides and mixtures thereof containing
two, generally from 2 to 8 and preferably from 2 to 4 hydroxyl
groups. These compounds may be mixed with other low molecular
weight polyfunctional compounds, such as polyols (preferred),
polyamines or polyhydrazides, having molecular weights in the range
from about 62 to 400. Such low molecular weight polyfunctional
polyols are generally included to modify the properties of the
product polyurethane.
The polyethers containing at least 2, generally from 2 to 8 and
preferably 2 or 3 hydroxyl groups are preferably used as the
reactive hydrogen-containing compound in the production of
polyurethanes. Appropriate polyethers are known to those in the
art. Such polyethers may be obtained by polymerizing epoxides, such
as ethylene oxide, propylene oxide, butylene oxide,
tetrahydrofuran, styrene oxide or epichlorohydrin. This
polymerization may be carried out using only the epoxide or by
addition of these epoxides (preferably ethylene oxide and propylene
oxide) to starter components. The epoxides may be used in admixture
(e.g., in a ratio of from 5:95 to 95:5) or added successively.
Appropriate starter components contain reactive hydrogen atoms and
include compounds such as water, alcohols, ammonia and amines.
Specific examples of starter components are: ethylene glycol; 1,3-
or 1,2-propylene glycol; trimethylol propane; glycerol; sorbitol;
4,4'-dihydroxy diphenyl propane; aniline; ethanolamine; and
ethylene diamine. It is also possible to use sucrose polyesters and
formitol-started or formose-started polyethers. In many cases, it
is preferred to use polyethers which contain predominantly primary
OH-groups (up to 90 wt. %, based on all the OH-groups present in
the polyether).
Polyesters containing hydroxyl groups which may be used to produce
polyurethanes include the reaction products of polyhydric
(preferably dihydric and even trihydric) alcohols with polybasic
(preferably dibasic) aliphatic, cycloaliphatic, aromatic and/or
heterocyclic carboxylic acids. Appropriate carboxylic acids are
adipic acid, sebacic acid, isophthalic acid, trimellitic acid,
phthalic acid anhydride, hexahydrophthalic acid anhydride,
tetrachlorophthalic acid anhydride, endomethylene
tetrahydrophthalic acid anhydride, fumaric acid, dimerized or
trimerized unsaturated fatty acids, terephthalic acid dimethyl
ester and terephthalic acid-bis-glycol ester. Suitable polyhydric
alcohols include: ethylene glycol, 1,2-propane diol, 1,3-propane
diol, 1,4-butane diol, 2,3-butane diol, 1,6-hexane diol, 1,8-octane
diol, neopentyl glycol, 1,4-bis-hydroxy methyl cyclohexane,
2-methyl-1,3-propane diol, glycerol, trimethylol propane,
1,2,6-hexane triol, trimethylol ethane, pentaerythritol, sorbitol,
formitol, methyl glycoside, di-, tri-, tetra- and higher
polyethylene glycols, propylene glycols and butylene glycols.
Polyesters of lactones (e.g., .epsilon.-caprolactone) or of hydroxy
carboxylic acids (e.g., .omega.-hydroxy caproic acid) may also be
used. Mixtures of 2 or more polyols or 2 or more carboxylic acids
should be used in cases where it is desired to obtain liquid
polyester polyols. Other suitable polyhydroxyl compounds are
described at pages 11 to 21 of German Offenlegungsschrift No.
2,854,384.
Other compounds containing at least 2 isocyanate-reactive hydrogen
atoms and having a molecular weight in the range from 62 to 400 may
also be used as reactive components for the production of
polyurethanes in accordance with the present invention. Such
compounds include those containing hydroxyl groups and also
compounds containing amino groups and/or thiol groups and/or
carboxyl groups and/or hydrazide terminal groups, which are known
as chain-extending agents or cross-linking agents. These compounds
generally contain from 2 to 8 (preferably from 2 to 4)
isocyanate-reactive hydrogen atoms, particularly hydroxyl groups.
It is possible to use mixtures of these compounds having a
molecular weight in the range from 62 to 400. Examples of such
compounds are ethylene glycol, 1,2-propane diol, 2,3-butane diol,
1,4-butane diol, neopentyl glycol, 1,4-bis-hydroxymethyl
cyclohexane, 2-methyl-1,3-propane diol, dibromobutene diol,
trimethylol propane, pentaerythritol, quinitol, sorbitol, castor
oil, diethylene glycol, 4,4'-dihydroxy diphenyl propane, dihydroxy
ethyl hydroquinone, ethanolamine, diethanolamine, N-methyl
diethanolamine, N-tert.-butyl-di-(.beta.-hydroxypropylamine),
triethanolamine and 3-aminopropanol. Examples of other such
compounds are given on pages 20 to 26 of German Offenlegungsschrift
No. 2,854,384.
Additionally, compounds having a functionality of 1 with respect to
isocyanates may be used as chain terminators. Monoamines such as
butyl or dibutyl amine, stearyl amine, N-methyl stearyl amine,
piperidine, cyclohexyl amine; or monoalcohols, such as butanol,
2-ethyl hexanol, ethylene glycol monomethyl ether, may be used as
chain terminators in quantities of from 0.01 to 10 wt. % (based on
polyurethane solids).
It is also possible to use catalysts known to those in the art in
the production of polyurethanes in accordance with the present
invention. Tertiary amines, such as triethyl amine, n-methyl
morpholine, tetramethyl ethylene diamine,
1,4-diazabicyclo-(2,2,2)octane,
bis-(dimethylaminoalkyl)-piperazines, dimethyl benzylamine,
1,2-dimethyl imidazole, monocyclic and bicyclic amidines,
bis-(dialkylaminoalkylethers) and tertiary amines containing amide
(preferably formamide) groups are appropriate catalysts.
Organometallic compounds, such as organic tin(II)compounds, are
particularly useful catalysts. In addition to sulfur-containing
compounds, such as dioctyl tin mercaptide, organotin compounds
which may be used as catalysts are tin(II)salts of carboxylic
acids, such as tin(II)acetate, tin(II)ethyl hexoate; and
tin(IV)compounds, for example dibutyl tin dichloride, dibutyl tin
diacetate, dibutyl tin dilaurate or dibutyl tin maleate. All of
these catalysts may, of course, be used in the form of mixtures.
Other examples of catalysts suitable for use in the practice of the
present invention and information on the way in which they function
can be found in Vieweg and Hochtlen's Kunststoffhandbuch, Vol. VII,
Carl-Hanser-Verlag, Munich, 1966, for example on pages 96 to 102,
and in German Offenlegungsschrift No. 2,854,384.
Known additives and auxiliaries may also be used to make
polyurethanes from the polymer polyether polyamines of the present
invention. Specifically, inorganic or organic substances which act
as blowing agents, for example, methylene chloride,
monofluorotrichloromethane, dichlorodifluoromethane, air, CO.sub.2
and oxides of nitrogen are useful.
Surface-active additives, such as emulsifiers and foam initiators
as well as foam stabilizers and reaction retarders may be employed
in accordance with techniques known to those in the art. It is
possible to use known cell regulators (such as paraffins or fatty
alcohols or dimethyl polysiloxanes) as well as pigments or dyes
and/or flameproofing agents, stabilizers against the effects of
ageing and weather, plasticizers, fungistatic and/or bacteriostatic
substances and fillers. Specific examples of such auxiliaries and
additives are found on pages 26 to 31 of German Offenlegungsschrift
No. 2,854,384 and in the literature references cited therein.
Polyurethane foams made from the polymer polyether polyamines of
the present invention may be produced in accordance with techniques
known to those in the art both in the form of free foams and in the
form of molded foams. Such foams may be produced by block foaming
or by known laminator processes or by any other technique known to
those skilled in foam-manufacturing technology.
Polyurethane elastomers may be produced from the polymer polyether
polyols of the present invention by casting, centrifugal casting or
spraying with manual or machine mixing of the components in
accordance with techniques known to those in the art.
The polymer polyether polyamines of the present invention should
preferably be mixed with other polyols of relatively high molecular
weight when used in making polyurethanes. In general, the
polyamines of the present invention yield polyurethane products
characterized by particularly high thermal stability, increased
modulus and an improved resistance to hot water.
The invention is illustrated by the following Examples in which the
quantities given represent parts by weight and percentages by
weight, unless otherwise indicated.
EXAMPLES
EXAMPLE 1
1.1 Production of the NCO-prepolymer
900 g of a polymer polyol were added dropwise over a period of 90
minutes at 80.degree. to 85.degree. C. to 106 g (0.61 mole) of
2,4-diisocyanatotoluene. This mixture was then stirred for 120
minutes at that temperature. The polymer polyol used was
difunctional, had an OH-number of 37, a viscosity of 1400 mPas at
25.degree. C. and a polymer content of 34.6%. This polymer polyol
was obtained by grafting a styrene/acrylonitrile (40:60) copolymer
onto a 1,2-propylene-glycol-started polypropylene oxide ether
having an OH-number of 56.
1.2 Production of the carbamate
A solution of the NCO-prepolymer of 1.1 (NCO content 2.74%) in 800
ml of dioxane was added dropwise over a period of 45 minutes at an
internal temperature of 10.degree. to 23.degree. C. to a solution
of 42.5 g of KOH (0.76 mole, OH:NCO =1.16) and 0.5 g of
Mersolat.RTM.-H (as emulsifier) in 150 ml of water. This mixture
was stirred for 10 minutes at the internal temperature of
10.degree. to 23.degree. C.
1.3 Production of the amine
650 ml of Lewatit.RTM.SPC 118 (ion exchanger) were added to the
reaction mixture of 1.2. The evolution of CO.sub.2 intensified
after heating to 60.degree. C. 14 liters of CO.sub.2 were given off
over a period of 3 hours (theoretical yield=14.6 1). After
separation of the ion exchanger by filtration, the filtrate was
freed from the solvent at 100.degree. C./18 mbar and then at
100.degree. C./0.8 mbar, leaving 870 g (88% of the theoretical
yield) of a yellow product.
Product characterization
% by weight of NH2 in the polymer polyether polyamine: 0.91
NH-number: 36.55 (theoretical value: 34)
Acid number: 2.1
Molecular weight (*): 3300 (theoretical value: 3296)
H.sub.2 O (determined by Karl Fischer's method): 0.29%
Viscosity: 300 Pas (visco-elastic) (*) as determined by vapor
pressure osmometry in toluene
Lewatit.RTM.SPC 118 (a product of Bayer AG) is a strongly acid
cation exchanger containing --SO.sub.3 H-- groups in a
styrene/divinyl benzene matrix (DVB-content 18%). The
macroporous/large-pored exchanger has a particle size distribution
of from 0.3 to 1.5 mm and a total capacity of 1.4 to 1.5
milliequivalents per ml.
The above-described procedure was repeated using the following ion
exchange resins: Lewatit SPC 108; SC 108; SC 104 and CNP 80. In
each case, the product polyamine was obtained in yield and purity
comparable to those of the product of Example 1. Information on
these ion exchangers can be found in the relevant prospectuses
published by Bayer AG, for example in the prospectus published on
Aug. 1, 1979 under number OC/I 20 233.
EXAMPLE 2
2.1 Production of the NCO-prepolymer
1000 g of a polymer polyol were added dropwise over a period of 180
minutes at 80.degree. C. to 86 g (0.49 mole) of
2,4-diisocyanatotoluene. This mixture was then stirred for 120
minutes at that temperature (i.e., 80.degree. C.). The polymer
polyol used was trifunctional, had an OH-number of 28, a viscosity
of 1900 mPas/25.degree. C. and a polymer content of 20%. The
polymer was a styrene/acrylonitrile (40:60) copolymer which was
radically grafted onto a trimethylol-propane-started polyether
containing 83% of propylene oxide and 17% of ethylene oxide
(OH-number 35).
2.2 Production of the carbamate
A solution of the NCO-prepolymer prepared in 2.1 (NCO-content 2.2%)
in 600 ml of dioxane was added dropwise over a period of 45 minutes
at an internal temperture of 18.degree. to 20.degree. C. to a
solution of 37 g (0.66 mole) of KOH and 0.5 g of Mersolat H in 150
ml of water. This mixture was stirred for 15 minutes at an internal
temperature of 18.degree. to 20.degree. C.
2.3 Production of the amine
700 ml of Lewatit SPC 118 were rapidly added to the reaction
mixture of 2.2. After heating to 60.degree. C., followed by
addition of 500 ml of dioxane, 11.2 liters of CO.sub.2
(theoretical: 12.75 1) were rapidly given off (80 minutes). After
the ion exchanger had been separated off by filtration, the solvent
was removed by distillation at 100.degree. C./17 mbar and
100.degree. C./0.13 mbar. 899 g (85% of theoretical yield) of a
yellow product having a salve-like consistency were obtained.
Product data
% of NH2 in the polymer polyether polyamine: 0.645
NH-number: 25.8 (theoretical 26.1)
Acid number: 0.9
Molecular weight: 6390 (theoretical 6438)
H.sub.2 O (Karl Fischer's method): 0.21%.
EXAMPLE 3
3.1 Production of the polymer polyol
The polymer polyol used was trifunctional, had an OH-number of
42.3, a solids content (polymer fraction) of 18.7% (14.8% of
acrylonitrile, 3.9% of styrene) and a viscosity of 2600 mPas at
20.degree. C. This polymer polyol was prepared as follows:
12 kg of a glycerol-started polyoxy propylene ether triol
containing 5% of terminal polyoxy ethylene blocks and having an
OH-number of 56 were heated under nitrogen to 120.degree. C. in a
100 liter capacity VA-autoclave equipped with a stirrer, reflux
condenser, gas inlet pipe and a monomer feed unit. A mixture of 36
kg of this polyether triol, 2.4 kg of styrene, 9.6 kg of
acrylonitrile and 120 g of azoisobutyronitrile (1%, based on
monomer) were introduced into the autoclave over a period of 4
hours through a membrane metering pump with the temperature being
maintained between 120.degree. C. and 125.degree. C. On completion
of the addition, the reaction mixture was stirred for 3 hours at
120.degree. C., after which a water jet vacuum was applied and all
the volatile constituents were distilled off over a period of 7
hours, ultimately in an oil pump vacuum of 0.8 mbar. 950 g of a
distillate containing 88.2% of acrylonitrile and 11.5% of styrene
was condensed. The product data were as follows: monomer conversion
92.1%, acrylonitrile bound 14.8%, styrene bound 3.9%, solids
content (polymer fraction) 18.7%.
3.2 Production of the NCO-prepolymer
1000 g of the polymer polyol of 3.1 were added dropwise over a
period of 180 minutes at 80.degree. C. to 131.4 g (0.755 mole) of
2,4-diisocyanatotoluene. This mixture was stirred for 120 minutes
at that temperature. The NCO-prepolymer had an NCO-content of
3.0%.
3.3 Production of the carbamate
A solution of the prepolymer of 3.2 in 750 ml of dioxane was added
dropwise over a period of 60 minutes at 20.degree. to 25.degree. C.
to a solution of 55 g (0.98 mole) of KOH and 0.5 g of
Mersolat.RTM.-H in 150 ml of water. This mixture was stirred for 15
minutes at an internal temperature of 20.degree. to 25.degree.
C.
3.4 Production of the amine
1.2 liters of Lewatit.RTM.SPC 118 were added to the above reaction
mixture over a period of 5 minutes. After heating to 60.degree. C.,
followed by the addition of 500 ml of dioxane, 14.8 liters of
CO.sub.2 (theoretical 16.9 liters) were rapidly given off (45
minutes). After the evolution of gas had stopped, the ion exchanger
was filtered off and the solvent was distilled off at 100.degree.
C./17 mbar and then at 100.degree. C./0.14 mbar. A pale yellow
product having a salve-like consistency was obtained in a quantity
of 1070 g (93.5% of the theoretical yield).
Product Data
% by weight of NH2 in the polymer polyether polyamine: 0.93
NH-number: 37.3
Acid number: 0.2
Molecular weight: 4500
H.sub.2 O (Karl Fischer's method): 0.1%.
EXAMPLE 4
4.1 Production of the NCO-prepolymer
4000 g of a polymer polyol were added dropwise over a period of 180
minutes at 80.degree. C. to 245 g (1.4 moles) of
2,4-diisocyanatotoluene. The temperature was then maintained at
80.degree. C. for 180 minutes. The NCO-prepolymer had an
NCO-content of 1.8%. The polymer polyol used was trifunctional, had
an OH-number of 19.7, a viscosity of 3800 mPas/20.degree. C. and a
polymer content of 28.6%. It was obtained by grafting 16.7% of
acrylonitrile and 11.9% of styrene onto a
trimethylol-propane-started polyether of 87% of ethylene oxide and
13% of propylene oxide (OH-number 28).
4.2 Production of the carbamate
A solution of the prepolymer of 4.1 in 5 liters of dioxane was
added dropwise over a period of 90 minutes at an internal
temperature of 20.degree. to 25.degree. C. to a solution of 102 g
(1.82 moles) of KOH and 1.5 g of Mersolat.RTM.H in 750 g of water.
This mixture was stirred for 35 minutes at an internal temperature
of 20.degree. to 25.degree. C.
4.3 Production of the amine
2.2 liters of Lewatit.RTM.SPC 118 (moist product) were added to the
reaction mixture of 4.2 over a period of 5 minutes. After heating
to 60.degree. C., followed by the addition of 1 liter of methanol,
29.8 liters of CO.sub.2 (theoretical yield: 31.4 liters) were
rapidly given off (30 minutes). After the evolution of gas had
stopped, the ion exchange resin was filtered off and the solvent
was distilled off at 100.degree. C./0.13 mbar. 3.9 kg (90% of
theoretical yield) of a yellow product having a salve-like
consistency were obtained.
Product data
% by weight of NH.sub.2 : 0.465
NH-number: 18.6
Acid number: 0.01
Molecular weight: 9000
H.sub.2 O (Karl Fischer's method): 0.3
EXAMPLE 5
5.1 Production of the NCO-prepolymer
2 kg of a polymer polyol were added dropwise over a period of 150
minutes at 80.degree. C. to 130.5 g (0.75 mole) of
2,4-diisocyanatotoluene. The temperature was then maintained at
180.degree. C. for 120 minutes by which time the NCO-content
amounted to 1.7%.
The polymer polyol used was difunctional, had an OH-number of 21, a
viscosity of 3800 mPas/20.degree. C. and a polymer content of 24.8%
(12.5% of acrylonitrile, 12.3% of styrene). It was obtained by
grafting acrylonitrile/styrene onto a 1,2-propylene-glycol-started
polyether containing 85% by weight of propylene oxide and 15% by
weight of ethylene oxide (OH-number 28).
5.2 Production of the carbamate
The prepolymer of 5.1 was heated to 75.degree. C. and then added
dropwise over a period of 120 minutes at an internal temperature of
25.degree.-30.degree. C. to a solution of 54.6 g (0.98 mole) of KOH
and 2 g of Mersolat.RTM.H in 2 liters of water. This mixture was
stirred for 35 minutes. 3 liters of methanol were then added.
5.3 Production of the amine
1.2 liters of Lewatit.RTM.SPC 118 (moist product) were added to the
reaction mixture of 5.2 over a period of 5 minutes. The evolution
of CO.sub.2, which began spontaneously after addition of the ion
exchanger, was completed by heating the mixture to 50.degree. C.
16.1 liters (96% of theoretical yield) of CO.sub.2 were given off
over a period of 60 minutes. After the evolution of CO.sub.2 had
stopped, the ion exchange resin (charged K+-form) was filtered off.
The filtrate gave two phases of which the lower methanol phase was
freed from the solvent by distillation at 100.degree. C./18 mbar
and 100.degree. C./0.15 mbar.
1950 g (94% of theoretical yield) of a yellow, salve-like product
were obtained.
Product data
% by weight of NH.sub.2 : 0.46
NH-number: 18.4
Acid number: 0.05
Molecular weight: 6000
H.sub.2 O (Karl Fischer's method): 0.28%
EXAMPLE 6
6.1 Production of the NCO-prepolymer
2000 g of a polymer polyol were added dropwise over a period of 240
minutes at 60.degree. C. to 176 g (1.01 mole) of
2,4-diisocyanatotoluene. The temperature was then maintained at
60.degree. C. for 240 minutes.
The polymer polyol used was trifunctional, had an OH-number of
28.3, a solids content of 19.1%
(acrylonitrile:methylmethacrylate=48:52) and a viscosity of 2640
mPas at room temperature. The starting polyether triol was obtained
by addition of propylene oxide and ethylene oxide with trimethylol
propane and had an OH-number of 35.
6.2 Production of the carbamate
A solution of the NCO-prepolymer of 6.1 in 1 liter of dioxane was
added dropwise over a period of 60 minutes at an internal
temperature of 18.degree. to 23.degree. C. to a solution of 221 g
(3.94 moles) of KOH and 1 g of Mersolat.RTM.K in 1500 ml of water.
This mixture was stirred for 30 minutes at an internal temperature
of 18.degree. to 23.degree. C.
6.3 Production of the amine
4.8 liters of Lewatit.RTM.SPC 118 (moist product) were added to the
reaction mixture of 6.2 over a period of 15 minutes. After heating
to 60.degree. C., followed by the addition of 1.8 liter of
methanol, 21 liters of CO.sub.2 (93% of theoretical yield) were
rapidly given off (38 minutes). After the evolution of gas had
stopped, the charged ion exchange resin was filtered off and the
solvent distilled off at 100.degree. C./18 mbar and then at
100.degree. C./0.25 mbar. 2.04 kg (95% of theoretical yield) of a
yellow-tinged, salve-like material characterized by the following
data were obtained:
% by weight of NH.sub.2 : 0.547
NH-number: 21.9
Acid number: 0.01
Molecular weight: 7700
H.sub.2 O (Karl Fischer's method): 0.18%.
EXAMPLE 7
This example illustrates use of the polymer polyamines of the
present invention in making a flexible cold foam.
7.1 Comparison Example (using known normal polyols)
Formulation:
polyol component mixture
75 parts of polyol I
25 parts of polyol II
3.1 parts of water
1.0 part of Dabco 33LV.RTM. (an amine catalyst manufactured by Air
Products)
1.5 parts of PU 3117 (a flexible foam catalyst manufactured by
Bayer AG)
0.4 part of KS 43 (a mixture of low molecular weight alkylated
siloxanes as foam stabilizer: manufacturer--Bayer AG)
Diisocyanate component
80 parts of isocyanate III
20 parts of isocyanate IV
Polyol I: a sorbitol-started polypropylene polyethylene glycol
ether having an OH-number of 28
Polyol II: a 1,2-propylene-glycol-started polypropylene glycol
ether having an OH-number of 48
Isocyanate III: an isocyanate mixture having an NCO content of 32.5
obtained by phosgenating the reaction product of aniline and
formaldehyde
Isocyanate IV: a mixture of 65% of 2,4-diisocyanatotoluene and 35%
of 2,6-diisocyanatotoluene having an NCO-content of 48.3%.
107 parts of the polyol component mixture described above were
mixed with 48.5 parts of diisocyanate component using a high-speed
stirrer (NCO-index 90). The resulting mixture was left to foam
freely. A foam having a gross density of 40 kg/m.sup.3 and a
compression hardness of 3.05 kPa (40% deformation) was
obtained.
7.2 Comparison Example (using polymer polyols)
Polyol II in the polyol component mixture described above in 7.1
was completely replaced by the same quantity (in parts by weight)
of the polymer polyol used in Example 1.1. The procedure of 7.1 was
repeated using this polyol component mixture. A foam having a gross
density of 40 kg/m.sup.3 and a compression hardness of 4.0 kPa (40%
deformation) was obtained.
7.3 (polymer polyamines of the present invention)
Half the quantity (in parts by weight) of polyol II in the polyol
component mixture described in 7.1 was replaced by the polymer
polyamine of Example 1. The procedure of Example 7.1 was repeated
using the polyol component mixture. The product foam had a
considerably improved compression hardness of 8.83 kPa (40%
deformation) and a gross density of 40 kg/m.sup.3.
Although the invention has been described in detail in the
foregoing for the purpose of illustration, it is to be understood
that such detail is solely for that purpose and that variations can
be made therein by those skilled in the art without departing from
the spirit and scope of the invention except as it may be limited
by the claims.
* * * * *